JP2021049697A - Curable resin composition for lining material, lining material, and method for repairing pipeline using the same - Google Patents
Curable resin composition for lining material, lining material, and method for repairing pipeline using the same Download PDFInfo
- Publication number
- JP2021049697A JP2021049697A JP2019173809A JP2019173809A JP2021049697A JP 2021049697 A JP2021049697 A JP 2021049697A JP 2019173809 A JP2019173809 A JP 2019173809A JP 2019173809 A JP2019173809 A JP 2019173809A JP 2021049697 A JP2021049697 A JP 2021049697A
- Authority
- JP
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- Prior art keywords
- lining material
- resin composition
- curable resin
- mass
- pipeline
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
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- 239000011342 resin composition Substances 0.000 title claims abstract description 51
- 239000000463 material Substances 0.000 title claims abstract description 45
- 238000000034 method Methods 0.000 title claims description 15
- 239000000178 monomer Substances 0.000 claims abstract description 17
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims abstract description 12
- 229920005989 resin Polymers 0.000 claims abstract description 12
- 239000011347 resin Substances 0.000 claims abstract description 12
- 239000003505 polymerization initiator Substances 0.000 claims abstract description 10
- 229920001567 vinyl ester resin Polymers 0.000 claims abstract description 9
- 229920006337 unsaturated polyester resin Polymers 0.000 claims abstract description 6
- 239000001913 cellulose Substances 0.000 claims description 10
- 229920002678 cellulose Polymers 0.000 claims description 10
- 239000002121 nanofiber Substances 0.000 claims description 10
- 229920001225 polyester resin Polymers 0.000 claims description 4
- 239000004645 polyester resin Substances 0.000 claims description 4
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 abstract description 26
- -1 hydride bisphenol Chemical compound 0.000 description 11
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 10
- 229920006305 unsaturated polyester Polymers 0.000 description 10
- 239000003795 chemical substances by application Substances 0.000 description 6
- 239000000843 powder Substances 0.000 description 6
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- TXBCBTDQIULDIA-UHFFFAOYSA-N 2-[[3-hydroxy-2,2-bis(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propane-1,3-diol Chemical compound OCC(CO)(CO)COCC(CO)(CO)CO TXBCBTDQIULDIA-UHFFFAOYSA-N 0.000 description 3
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- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 3
- 239000012965 benzophenone Substances 0.000 description 3
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- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 2
- QEQBMZQFDDDTPN-UHFFFAOYSA-N (2-methylpropan-2-yl)oxy benzenecarboperoxoate Chemical compound CC(C)(C)OOOC(=O)C1=CC=CC=C1 QEQBMZQFDDDTPN-UHFFFAOYSA-N 0.000 description 1
- MUTGBJKUEZFXGO-OLQVQODUSA-N (3as,7ar)-3a,4,5,6,7,7a-hexahydro-2-benzofuran-1,3-dione Chemical compound C1CCC[C@@H]2C(=O)OC(=O)[C@@H]21 MUTGBJKUEZFXGO-OLQVQODUSA-N 0.000 description 1
- KMOUUZVZFBCRAM-OLQVQODUSA-N (3as,7ar)-3a,4,7,7a-tetrahydro-2-benzofuran-1,3-dione Chemical compound C1C=CC[C@@H]2C(=O)OC(=O)[C@@H]21 KMOUUZVZFBCRAM-OLQVQODUSA-N 0.000 description 1
- ZQHJVIHCDHJVII-OWOJBTEDSA-N (e)-2-chlorobut-2-enedioic acid Chemical compound OC(=O)\C=C(\Cl)C(O)=O ZQHJVIHCDHJVII-OWOJBTEDSA-N 0.000 description 1
- MYWOJODOMFBVCB-UHFFFAOYSA-N 1,2,6-trimethylphenanthrene Chemical compound CC1=CC=C2C3=CC(C)=CC=C3C=CC2=C1C MYWOJODOMFBVCB-UHFFFAOYSA-N 0.000 description 1
- VNQXSTWCDUXYEZ-UHFFFAOYSA-N 1,7,7-trimethylbicyclo[2.2.1]heptane-2,3-dione Chemical compound C1CC2(C)C(=O)C(=O)C1C2(C)C VNQXSTWCDUXYEZ-UHFFFAOYSA-N 0.000 description 1
- QZKVUSSYPPWURQ-UHFFFAOYSA-N 1-methylthioxanthen-9-one Chemical compound S1C2=CC=CC=C2C(=O)C2=C1C=CC=C2C QZKVUSSYPPWURQ-UHFFFAOYSA-N 0.000 description 1
- JCTXKRPTIMZBJT-UHFFFAOYSA-N 2,2,4-trimethylpentane-1,3-diol Chemical compound CC(C)C(O)C(C)(C)CO JCTXKRPTIMZBJT-UHFFFAOYSA-N 0.000 description 1
- PIZHFBODNLEQBL-UHFFFAOYSA-N 2,2-diethoxy-1-phenylethanone Chemical compound CCOC(OCC)C(=O)C1=CC=CC=C1 PIZHFBODNLEQBL-UHFFFAOYSA-N 0.000 description 1
- 125000004098 2,6-dichlorobenzoyl group Chemical group O=C([*])C1=C(Cl)C([H])=C([H])C([H])=C1Cl 0.000 description 1
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 description 1
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 1
- FDSUVTROAWLVJA-UHFFFAOYSA-N 2-[[3-hydroxy-2,2-bis(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propane-1,3-diol;prop-2-enoic acid Chemical compound OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.OCC(CO)(CO)COCC(CO)(CO)CO FDSUVTROAWLVJA-UHFFFAOYSA-N 0.000 description 1
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- KMNCBSZOIQAUFX-UHFFFAOYSA-N 2-ethoxy-1,2-diphenylethanone Chemical class C=1C=CC=CC=1C(OCC)C(=O)C1=CC=CC=C1 KMNCBSZOIQAUFX-UHFFFAOYSA-N 0.000 description 1
- IQQVCMQJDJSRFU-UHFFFAOYSA-N 2-ethyl-2-(hydroxymethyl)propane-1,3-diol;prop-2-enoic acid Chemical compound OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.CCC(CO)(CO)CO IQQVCMQJDJSRFU-UHFFFAOYSA-N 0.000 description 1
- WDQMWEYDKDCEHT-UHFFFAOYSA-N 2-ethylhexyl 2-methylprop-2-enoate Chemical compound CCCCC(CC)COC(=O)C(C)=C WDQMWEYDKDCEHT-UHFFFAOYSA-N 0.000 description 1
- WFUGQJXVXHBTEM-UHFFFAOYSA-N 2-hydroperoxy-2-(2-hydroperoxybutan-2-ylperoxy)butane Chemical compound CCC(C)(OO)OOC(C)(CC)OO WFUGQJXVXHBTEM-UHFFFAOYSA-N 0.000 description 1
- NLGDWWCZQDIASO-UHFFFAOYSA-N 2-hydroxy-1-(7-oxabicyclo[4.1.0]hepta-1,3,5-trien-2-yl)-2-phenylethanone Chemical compound OC(C(=O)c1cccc2Oc12)c1ccccc1 NLGDWWCZQDIASO-UHFFFAOYSA-N 0.000 description 1
- KIHBGTRZFAVZRV-UHFFFAOYSA-N 2-hydroxyoctadecanoic acid Chemical compound CCCCCCCCCCCCCCCCC(O)C(O)=O KIHBGTRZFAVZRV-UHFFFAOYSA-N 0.000 description 1
- BQZJOQXSCSZQPS-UHFFFAOYSA-N 2-methoxy-1,2-diphenylethanone Chemical class C=1C=CC=CC=1C(OC)C(=O)C1=CC=CC=C1 BQZJOQXSCSZQPS-UHFFFAOYSA-N 0.000 description 1
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- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 1
- HNEGQIOMVPPMNR-UHFFFAOYSA-N methylfumaric acid Natural products OC(=O)C(C)=CC(O)=O HNEGQIOMVPPMNR-UHFFFAOYSA-N 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- 238000005580 one pot reaction Methods 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 239000011435 rock Substances 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- 230000008719 thickening Effects 0.000 description 1
- 238000005809 transesterification reaction Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 150000004072 triols Chemical class 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
- 239000002025 wood fiber Substances 0.000 description 1
Landscapes
- Lining Or Joining Of Plastics Or The Like (AREA)
- Pipe Accessories (AREA)
- Macromonomer-Based Addition Polymer (AREA)
Abstract
Description
本発明は、管路の内壁面を被覆するためのライニング材用硬化性樹脂組成物、ライニング材及びこれを用いた管路補修方法に関する。 The present invention relates to a curable resin composition for a lining material for covering the inner wall surface of a pipeline, a lining material, and a pipeline repair method using the same.
下水道管などの管路は、長年の使用により腐食やひび割れなどが生じるため、所定の時期に補修を行う必要がある。補修方法には様々な方法が存在するが、一般的な手法として、管路の内壁面を樹脂製のライニング材で被覆する手法が補修効果及び作業効率の点から用いられている。この手法では、硬化前のライニング材で構造物内面を被覆し、その状態で光照射または加熱によりライニング材に含まれる硬化性樹脂組成物を硬化させることにより、既設の管路の内側に樹脂製の更生管を形成する。 Since pipelines such as sewer pipes are corroded and cracked after many years of use, they need to be repaired at a predetermined time. There are various repair methods, but as a general method, a method of covering the inner wall surface of the pipeline with a resin lining material is used from the viewpoint of repair effect and work efficiency. In this method, the inner surface of the structure is covered with a lining material before curing, and in that state, the curable resin composition contained in the lining material is cured by light irradiation or heating, so that the inside of the existing pipeline is made of resin. Form a rehabilitation tube.
このようなライニング材用の硬化性樹脂組成物として、従来では、不飽和ポリエステル樹脂やビニルエステル樹脂などの重合性樹脂、スチレン及び重合開始剤を含む硬化性樹脂組成物が使用されている。 As the curable resin composition for such a lining material, a curable resin composition containing a polymerizable resin such as an unsaturated polyester resin or a vinyl ester resin, styrene, and a polymerization initiator has been conventionally used.
スチレンは臭気や有害性の問題があることから、近年ではスチレンを含まないいわゆるノンスチレンのライニング材用硬化性樹脂組成物の需要が高まっており、実際に開発されている。しかしながら、スチレンを含まない場合、硬化後の架橋密度（強度）が低下するという問題がある。また、従来のスチレンを使用したライニング材用硬化性樹脂組成物は、強度に優れるものの、柔軟性が不十分であり、地震などに由来する揺れに対する性能が不十分であった。 Since styrene has problems of odor and harmfulness, the demand for a so-called non-styrene curable resin composition for a lining material containing no styrene has been increasing in recent years, and it has been actually developed. However, when styrene is not contained, there is a problem that the crosslink density (strength) after curing decreases. Further, although the conventional curable resin composition for a lining material using styrene is excellent in strength, it is insufficient in flexibility and has insufficient performance against shaking caused by an earthquake or the like.
したがって、本発明の目的は、強度が高く、柔軟性に優れるノンスチレンのライニング剤用硬化性樹脂組成物を提供することにある。また、本発明の目的は、この硬化性樹脂組成物を含むライニング材、及びそのライニング材を使用する管路の補修方法を提供することにある。 Therefore, an object of the present invention is to provide a curable resin composition for a non-styrene lining agent having high strength and excellent flexibility. Another object of the present invention is to provide a lining material containing this curable resin composition and a method for repairing a pipeline using the lining material.
上記目的は、管路の内壁面を被覆するためのライニング材に含まれる硬化性樹脂組成物であって、
（Ａ）不飽和ポリエステル樹脂またはビニルエステル樹脂、
（Ｂ）３官能以上の（メタ）アクリレートモノマー、及び
（Ｃ）重合開始剤
を含む、ライニング材用硬化性樹脂組成物により達成される。
The above object is a curable resin composition contained in a lining material for covering the inner wall surface of a pipeline.
(A) Unsaturated polyester resin or vinyl ester resin,
It is achieved by a curable resin composition for a lining material, which comprises (B) a trifunctional or higher functional (meth) acrylate monomer and (C) a polymerization initiator.
好ましくは、ライニング材用硬化性樹脂組成物は（Ｄ）セルロースナノファイバーを更に含む。 Preferably, the curable resin composition for the lining material further comprises (D) cellulose nanofibers.
好ましくは、（Ｂ）３官能以上の（メタ）アクリレートモノマーの含有量が、（Ａ）ポリエステル樹脂またはビニルエステル樹脂１００質量部に対して、０．１〜２５質量部である。 Preferably, the content of (B) trifunctional or higher (meth) acrylate monomer is 0.1 to 25 parts by mass with respect to 100 parts by mass of (A) polyester resin or vinyl ester resin.
好ましくは、（Ｄ）セルロースナノファイバーの含有量が、（Ａ）ポリエステル樹脂またはビニルエステル樹脂１００質量部に対して、０．１〜５質量部である。 Preferably, the content of (D) cellulose nanofibers is 0.1 to 5 parts by mass with respect to 100 parts by mass of (A) polyester resin or vinyl ester resin.
また、上記目的は、本発明のライニング材用硬化性樹脂組成物を含むライニング材により達成される。 Further, the above object is achieved by the lining material containing the curable resin composition for the lining material of the present invention.
さらに、上記目的は、管路の内壁面を本発明のライニング材で被覆し、その状態で前記硬化性樹脂組成物を硬化させる工程を含む、管路の補修方法により達成される。 Further, the above object is achieved by a method for repairing a pipeline, which comprises a step of coating the inner wall surface of the pipeline with the lining material of the present invention and curing the curable resin composition in that state.
本発明によれば、架橋密度が高く、柔軟性に優れるノンスチレンのライニング剤用硬化性樹脂組成物を提供することができる。したがって、作業効率がよく、信頼性の高い管路の補修方法を提供することができる。 According to the present invention, it is possible to provide a curable resin composition for a non-styrene lining agent having a high crosslink density and excellent flexibility. Therefore, it is possible to provide a method for repairing a pipeline with good work efficiency and high reliability.
以下、本発明を詳細に説明する。本発明のライニング材用硬化性樹脂組成物は、上述したように、（Ａ）不飽和ポリエステル樹脂またはビニルエステル樹脂、（Ｂ）３官能以上の（メタ）アクリレートモノマー及び（Ｃ）重合開始剤を含み、更に必要に応じて、（Ｄ）セルロースナノファイバーや他の添加剤を含む。以下、各成分を詳細に説明する。 Hereinafter, the present invention will be described in detail. As described above, the curable resin composition for a lining material of the present invention contains (A) unsaturated polyester resin or vinyl ester resin, (B) trifunctional or higher (meth) acrylate monomer, and (C) polymerization initiator. Includes, and optionally (D) cellulose nanofibers and other additives. Hereinafter, each component will be described in detail.
［（Ａ）不飽和ポリエステル樹脂］
不飽和ポリエステルは、どのような不飽和ポリエステルを使用することができる。例えば、不飽和ポリエステルは、α、β−不飽和カルボン酸と多価アルコールとのエステル化反応、続いて脱グリコール反応によって得られる。α、β−不飽和カルボン酸以外にも飽和カルボン酸を含んでもよい。
[(A) Unsaturated polyester resin]
As the unsaturated polyester, any unsaturated polyester can be used. For example, unsaturated polyesters are obtained by esterification of α, β-unsaturated carboxylic acids with polyhydric alcohols, followed by deglycolation. Saturated carboxylic acid may be contained in addition to α and β-unsaturated carboxylic acid.
通常、オルソ系は１段反応、イソ系は２段反応、テレ系はエステル交換反応後にエステル化することができる。エステル化の際の反応温度は１９０〜２２０℃の範囲が望ましい。高反応性エステルを得るためには、２００℃以下が望ましい。窒素ガスを流入しながら、常法によりエステル化を進めることができる。 Usually, the ortho system can be esterified after the one-step reaction, the iso system can be esterified after the transesterification reaction, and the tele system can be esterified. The reaction temperature during esterification is preferably in the range of 190 to 220 ° C. In order to obtain a highly reactive ester, it is desirable that the temperature is 200 ° C. or lower. Esterification can be carried out by a conventional method while flowing in nitrogen gas.
得られる不飽和ポリエステルの酸価は特に限定されないが、例えば、５〜３０ＫＯＨｍｇ／ｇであり、特に１５〜３０ＫＯＨｍｇ／ｇが好ましい。酸価が低いので、熱可塑性樹脂粉末による増粘が特に有効である。また得られる不飽和ポリエステルの水酸基価は特に限定されないが、例えば１０〜２００ＫＯＨｍｇ／ｇであり、さらに１５〜１７０ＫＯＨｍｇ／ｇ、特に１５〜３０ＫＯＨｍｇ／ｇが好ましい。 The acid value of the obtained unsaturated polyester is not particularly limited, but is, for example, 5 to 30 KOH mg / g, particularly preferably 15 to 30 KOH mg / g. Since the acid value is low, thickening with a thermoplastic resin powder is particularly effective. The hydroxyl value of the obtained unsaturated polyester is not particularly limited, but is, for example, 10 to 200 KOH mg / g, more preferably 15 to 170 KOH mg / g, and particularly preferably 15 to 30 KOH mg / g.
α、β−不飽和カルボン酸の例としては、フマル酸、マレイン酸、無水マレイン酸、イタコン酸、シトラコン酸、メサコン酸、クロロマレイン酸、又はこれらのジメチルエステル類等を挙げることができる。これらのα、β−不飽和カルボン酸は、それぞれ単独で用いても、２種以上を組み合わせて用いてもよい。また、飽和カルボン酸としては、例えばフタル酸、無水フタル酸、イソフタル酸、テレフタル酸、ヘット酸、ヘキサヒドロ無水フタル酸、テトラヒドロ無水フタル酸、アジピン酸、セバチン酸等を使用することができる。これらの飽和カルボン酸はそれぞれ単独で用いてもよいし、２種以上を組み合わせてもよい。 Examples of α, β-unsaturated carboxylic acids include fumaric acid, maleic acid, maleic anhydride, itaconic acid, citraconic acid, mesaconic acid, chloromaleic acid, and dimethyl esters thereof. These α and β-unsaturated carboxylic acids may be used alone or in combination of two or more. As the saturated carboxylic acid, for example, phthalic acid, phthalic anhydride, isophthalic acid, terephthalic acid, hetic acid, hexahydrophthalic anhydride, tetrahydrophthalic anhydride, adipic acid, sebatic acid and the like can be used. Each of these saturated carboxylic acids may be used alone, or two or more thereof may be combined.
一方、多価アルコールとしては、例えば、エチレングリコール、ジエチレングリコール、プロピレングリコール、ジプロピレングリコール、トリメチレングリコール、１、３−ブタンジオール、１、４−ブタンジオール、２−メチル−１、３−プロパンジオール、１、６−ヘキサンジオール、シクロヘキサンジオール、ネオペンチルグリコール、２、２、４−トリメチル−１、３−ペンタンジオール、１、４−シクロヘキサンジメタノール、水素化ビスフェノールＡ、水素化ビスフェノールＡのアルキレンオキサイド付加物等のジオール類、トリメチロールプロパンなどのトリオール類、ペンタエリスリトール等のテトラオール類等を挙げることができる。これらの多価アルコール類はそれぞれ単独で用いても、２種以上を組み合わせて用いてもよい。 On the other hand, examples of the polyhydric alcohol include ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, trimethylene glycol, 1,3-butanediol, 1,4-butanediol, 2-methyl-1,3-propanediol. 1,6-hexanediol, cyclohexanediol, neopentyl glycol, 2,2,4-trimethyl-1,3-pentanediol, 1,4-cyclohexanedimethanol, hydride bisphenol A, alkylene oxide of hydride bisphenol A Examples thereof include diols such as additives, triols such as trimethylolpropane, and tetraols such as pentaerythritol. These polyhydric alcohols may be used alone or in combination of two or more.
また、ジシクロペンタジエンを添加し、上記α、β−不飽和カルボン酸、飽和カルボン酸及び多価アルコールと共に反応して得られるジシクロペンタジエン系不飽和ポリエステルも使用することができる。 Further, a dicyclopentadiene-based unsaturated polyester obtained by adding dicyclopentadiene and reacting with the above-mentioned α, β-unsaturated carboxylic acid, saturated carboxylic acid and polyhydric alcohol can also be used.
また、回収ポリエチレンテレフタレート（以下、ＰＥＴと略記）と多価アルコールを高温で反応させたグリコール分解物を主たる原料として、上記α、β−不飽和カルボン酸及び多価アルコールと共に反応して得られるＰＥＴ系不飽和ポリエステルも本発明の不飽和ポリエステルとして使用することができる。 Further, PET obtained by reacting with the above-mentioned α, β-unsaturated carboxylic acid and polyhydric alcohol using a glycol decomposition product obtained by reacting recovered polyethylene terephthalate (hereinafter abbreviated as PET) with a polyhydric alcohol at a high temperature as a main raw material. The unsaturated polyester system can also be used as the unsaturated polyester of the present invention.
（Ａ）不飽和ポリエステルの数平均分子量（Ｍｎ）は、特に限定されないが、取扱い良好な粘度の観点から、例えば、５００〜４０００の範囲であり、５００〜３０００の範囲が好ましい。 The number average molecular weight (Mn) of the unsaturated polyester (A) is not particularly limited, but is preferably in the range of 500 to 4000, preferably in the range of 500 to 3000, from the viewpoint of viscosity that is easy to handle.
（Ａ）不飽和ポリエステルの使用量は、本発明の硬化性樹脂組成物の全重量を基準として、３０〜７０質量％、好ましくは３５〜６５質量％である。 The amount of the unsaturated polyester (A) used is 30 to 70% by mass, preferably 35 to 65% by mass, based on the total weight of the curable resin composition of the present invention.
［（Ｂ）３官能以上の（メタ）アクリレートモノマー］
本発明で使用される（Ｂ）３官能以上の（メタ）アクリレートモノマーはどのようなものでもよいが、具体的には、ペンタエリスリトールトリ（メタ）アクリレート、トリメチロールプロパントリ（メタ）アクリレート、エトキシ化トリメチロールプロパントリ（メタ）アクリレート、トリメチロールプロパントリ（メタ）クリレート、ジトリメチロールプロパンテトラアクリレート、ペンタエリスリトールテトラアクリレート、エトキシ化ペンタエリスリトールテトラアクリレート、ジペンタエリスルトールペンタアクリレート、ジペンタエリスリトールペンタメタクリレート、ジペンタエリスリトールヘキサアクリレート、ジペンタエリスリトールヘキサメタクリレート、ジペンタエリスリトールポリアクリレート、エトキシ化ポリグリセリンポリアクリレート、エトキシ化ソルビトールポリアクリレートなどが挙げられる。（Ｂ）成分は４〜７官能が好ましく、更に５〜７官能が好ましく、特に５〜６官能が好ましい。
[(B) Trifunctional or higher (meth) acrylate monomer]
The (B) trifunctional or higher functional (meth) acrylate monomer used in the present invention may be any, but specifically, pentaerythritol tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, and ethoxy. Trimethylolpropane tri (meth) acrylate, trimethylolpropane tri (meth) crylate, trimethylolpropane tetraacrylate, pentaerythritol tetraacrylate, ethoxylated pentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol pentamethacrylate , Dipentaerythritol hexaacrylate, dipentaerythritol hexamethacrylate, dipentaerythritol polyacrylate, ethoxylated polyglycerin polyacrylate, ethoxylated sorbitol polyacrylate and the like. The component (B) is preferably 4 to 7 functional, more preferably 5 to 7 functional, and particularly preferably 5 to 6 functional.
（Ｂ）３官能以上の（メタ）アクリレートモノマーの含有量は、本発明の硬化性樹脂組成物の全重量を基準として、一般に０．１〜２５質量％、好ましくは５〜１５質量％である。 (B) The content of the trifunctional or higher functional (meth) acrylate monomer is generally 0.1 to 25% by mass, preferably 5 to 15% by mass, based on the total weight of the curable resin composition of the present invention. ..
［（Ｃ）重合開始剤］
重合開始剤は従来から使用されているものでよく、光重合開始剤や有機過酸化物が用いられる。光重合開始剤としては、公知の紫外線重合開始剤及び／又は硬化性複合材料が厚膜でも硬化できる可視光重合開始剤を使用できる。紫外線重合開始剤の例としては、ベンゾインエーテル系のイソプロピルベンゾインエーテル、イソブチルベンゾインエーテル、ベンゾインエチルエーテル、ベンゾインメチルエーテル、ベンジルケタール系のヒドロシクロヘキシルフェニルケトン、ベンジルジメチルケタール、ケトンベンゾフェノン系のベンジル、メチル−Ｏ−ベンゾインベンゾエート、２−クロロチオキサントン、メチルチオキサントン、ベンゾフェノン系のベンゾフェノン／第３級アミン、２，２−ジエトキシアセトフェノン、α−ヒドロキシイソブチルフェノン、アシロホスフィンオキサイド、ビスアシルホスフィンオキサイド、カンファーキノン等を代表例として挙げることができる。本発明に用いられる光硬化性の管状ライニング材の場合は管内部に紫外線を挿入して、紫外線を照射して速硬化する被覆方法がとられる。紫外光波長領域の２５０ｎｍから可視光波長領域の４５０ｎｍの吸収をもつ光重合開始剤が好ましい。２，４，６−トリメチルベンゾイルジフェニルホスフィンオキサイド、ベンジルメチルケタールが好ましく、単独使用又は併用してもよい。
[(C) Polymerization Initiator]
The polymerization initiator may be one that has been conventionally used, and a photopolymerization initiator or an organic peroxide is used. As the photopolymerization initiator, a known ultraviolet polymerization initiator and / or a visible photopolymerization initiator capable of curing even a thick film of a curable composite material can be used. Examples of UV polymerization initiators include benzoin ether-based isopropylbenzoin ethers, isobutylbenzoin ethers, benzoin ethyl ethers, benzoin methyl ethers, benzyl ketal-based hydrocyclohexylphenyl ketones, benzyl dimethyl ketals, ketone benzophenone-based benzyls, and methyl-. O-benzoin benzoate, 2-chlorothioxanthone, methylthioxanthone, benzophenone-based benzophenone / tertiary amine, 2,2-diethoxyacetophenone, α-hydroxyisobutylphenone, asylophosphine oxide, bisacylphosphine oxide, camphorquinone, etc. It can be mentioned as a typical example. In the case of the photocurable tubular lining material used in the present invention, a coating method is adopted in which ultraviolet rays are inserted into the tube and irradiated with ultraviolet rays to cure quickly. A photopolymerization initiator having an absorption of 250 nm in the ultraviolet light wavelength region to 450 nm in the visible light wavelength region is preferable. 2,4,6-trimethylbenzoyldiphenylphosphine oxide and benzylmethyl ketal are preferable, and they may be used alone or in combination.
また，可視光重合開始剤としては、アシルホスフィンオキサイド化合物が有効である。その例としては，ビス（２，６−ジクロルベンゾイル）−フェニルホスフィンオキサイド、ビス（２，６−ジクロルベンゾイル）−２，５−ジメチルフェニルホスフィンオキサイド、ビス（２，６−ジクロルベンゾイル）−４−エトキシフェニルホスフィンオキサイド、ビス（２，６−ジクロルベンゾイル）−４−プロピルフェニルホスフィンオキサイド、ビス（２，６−ジメトキシベンゾイル）−２，４，４−トリメチルペンチルホスフィンオキサイド、２，４，６−トリメチルベンゾイル−ジフェニルホスフィンオキサイド等を挙げることができる。単独使用又は併用してもよい。 Further, as the visible light polymerization initiator, an acylphosphine oxide compound is effective. Examples are bis (2,6-dichlorobenzoyl) -phenylphosphine oxide, bis (2,6-dichlorobenzoyl) -2,5-dimethylphenylphosphine oxide, bis (2,6-dichlorobenzoyl). -4-ethoxyphenylphosphine oxide, bis (2,6-dichlorobenzoyl) -4-propylphenylphosphine oxide, bis (2,6-dimethoxybenzoyl) -2,4,4-trimethylpentylphosphine oxide, 2,4 , 6-trimethylbenzoyl-diphenylphosphine oxide and the like. It may be used alone or in combination.
光重合開始剤の使用量は、本発明の硬化性樹脂組成物の全重量を基準として、例えば、０．０１〜５質量％の範囲である。 The amount of the photopolymerization initiator used is, for example, in the range of 0.01 to 5% by mass based on the total weight of the curable resin composition of the present invention.
有機過酸化物としては、ケトンパーオキサイド類、例えばメチルエチルケトンパーオキサイド等；ハイドロパーオキサイド類、例えばクメンハイドロパーオキサイド、ｔ−ブチルハイドロパーオキサイド等；パーオキシエステル類、例えばｔ−ブチルパーオキシオクトエート、ｔ−ブチルパーオキシベンゾエート等；ジアルキルパーオキサイド類、例えばジクミルパーオキサイド等；ジアシルパーオキサイド類、例えばラウロイルパーオキサイド、ベンゾイルパーオキサイド等を挙げることができる。 Examples of organic peroxides include ketone peroxides such as methyl ethyl ketone peroxide; hydroperoxides such as cumene hydrooxide and t-butyl hydroperoxide; peroxyesters such as t-butyl peroxyoctate. , T-Butyl peroxybenzoate and the like; dialkyl peroxides such as dicumyl peroxide and the like; diacyl peroxides such as lauroyl peroxide and benzoyl peroxide and the like can be mentioned.
有機過酸化物の使用量は、本発明の硬化性樹脂組成物の全重量を基準として、例えば、０．０１〜５質量％の範囲である。 The amount of the organic peroxide used is, for example, in the range of 0.01 to 5% by mass based on the total weight of the curable resin composition of the present invention.
［（Ｄ）セルロースナノファイバー］
セルロースナノファイバーとは、木材などから得られる木材繊維をナノオーダーのサイズまで微細化したバイオマス素材をいう。セルロースナノファイバーの数平均繊維径は、例えば、１〜１０００ｎｍ、好ましくは５〜５００ｎｍ、特に１０〜１００ｎｍであり、アスペクト比、例えば、１００以上、特に１００〜５００である。セルロースナノファイバーは化学的に修飾されたものでもよいし、修飾されていないものでもよい。
[(D) Cellulose nanofibers]
Cellulose nanofibers are biomass materials obtained by refining wood fibers obtained from wood or the like to nano-order size. The number average fiber diameter of the cellulose nanofibers is, for example, 1 to 1000 nm, preferably 5 to 500 nm, particularly 10 to 100 nm, and the aspect ratio, for example, 100 or more, particularly 100 to 500. Cellulose nanofibers may be chemically modified or unmodified.
（Ｄ）セルロースナノファイバーの含有量は、本発明の硬化性樹脂組成物の全重量を基準として、一般に０．０１〜５質量％、好ましくは０．１〜２質量％、更に好ましくは０．１〜１質量％、特に好ましくは０．１〜０．５質量％である。 The content of the cellulose nanofibers (D) is generally 0.01 to 5% by mass, preferably 0.1 to 2% by mass, more preferably 0.%, based on the total weight of the curable resin composition of the present invention. It is 1 to 1% by mass, particularly preferably 0.1 to 0.5% by mass.
［他の成分］
本発明で用いられる樹脂組成物は、その組成物単独でも使用できるが、シックハウス問題及び化学物質排出把握管理移動登録法（ＰＲＴＲ法）等によるスチレン排出濃度規制を考慮して、以下の架橋用重合性ビニルモノマーを併用して蒸気圧の高い架橋用重合性モノマーを大幅に削減した樹脂組成物として使用することもできる。
[Other ingredients]
The resin composition used in the present invention can be used alone, but in consideration of the sick house problem and the regulation of styrene emission concentration by the chemical substance emission grasp management transfer registration method (PRTR method), the following polymerization for cross-linking It can also be used as a resin composition in which a polymerizable monomer for cross-linking having a high vapor pressure is significantly reduced by using a sex vinyl monomer in combination.
架橋用重合性ビニルモノマーの例としては、スチレン、ビニルトルエン及びα−メチルスチレン等の芳香族ビニルモノマー；メチルメタクリレート、エチルメタクリレート、ｎ−ブチルメタクリレート、イソブチルメタクリレート、２−エチルヘキシルメタクリレート等のメタクリレート系モノマーを挙げることができる。これら架橋用重合性モノマーは、単独使用でも２種以上併用でもよい。一般的にはスチレンが使用される。架橋性重合性モノマーの配合量は、本発明の硬化性樹脂組成物の全重量を基準として、３０質量％（架橋用重合性モノマー含有率２３％以下）以下が好ましい。 Examples of polymerizable vinyl monomers for cross-linking include aromatic vinyl monomers such as styrene, vinyltoluene and α-methylstyrene; and methacrylate-based monomers such as methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, isobutyl methacrylate and 2-ethylhexyl methacrylate. Can be mentioned. These cross-linking polymerizable monomers may be used alone or in combination of two or more. Generally, styrene is used. The blending amount of the crosslinkable polymerizable monomer is preferably 30% by mass (content of the crosslinkable polymerizable monomer 23% or less) or less based on the total weight of the curable resin composition of the present invention.
本発明の樹脂組成物の成分のみで乾燥性に優れたことが特徴であるが、より乾燥性を向上させる目的でパラフィン及び／又はワックス類を併用してもよい。 The resin composition of the present invention is characterized by having excellent drying properties, but paraffin and / or waxes may be used in combination for the purpose of further improving the drying properties.
本発明の硬化性樹脂組成物に用いられるパラフィン及び／又はワックス類としては、パラフィンワックス、ポリエチレンワックスス等のパラフィン類；ステアリン酸、１、２−ヒドロキシステアリン酸等の高級脂肪酸等を挙げることができるが、パラフィンワックスが好ましい。このパラフィン及び／又はワックス類は、塗膜表面における硬化反応中の空気遮断作用、耐汚染性の向上を目的として添加される。添加率としては本発明の硬化性樹脂組成物の全重量を基準として、０．１〜５質量％、好ましくは０．２〜２質量％である。 Examples of paraffins and / or waxes used in the curable resin composition of the present invention include paraffin waxes such as paraffin wax and polyethylene wax; higher fatty acids such as stearic acid and 1,2-hydroxystearic acid. Although possible, paraffin wax is preferred. The paraffin and / or waxes are added for the purpose of improving the air blocking action and stain resistance during the curing reaction on the coating film surface. The addition rate is 0.1 to 5% by mass, preferably 0.2 to 2% by mass, based on the total weight of the curable resin composition of the present invention.
本発明で用いられる不活性な微粒子状及び／又は粒状の無機骨材材料としては、砂、シリカ粉末、粉砕岩石、炭酸カルシウム、アルミナ粉、クレー、珪石粉、タルク、ガラス粉、シリカパウダー、水酸化アルミニウム、珪砂、珪酸アルミニウム、珪酸マグネシウム、セメント等を使用することができる。 The inert fine and / or granular inorganic aggregate material used in the present invention includes sand, silica powder, crushed rock, calcium carbonate, alumina powder, clay, silica stone powder, talc, glass powder, silica powder, and water. Aluminum oxide, silica sand, aluminum silicate, magnesium silicate, cement and the like can be used.
不活性な微粒子状及び／又は粒状の無機質骨材材料を使用する際、その使用量は、熱硬化性樹脂組成物を繊維質筒状体に含浸した管体ライニング材の場合は、本発明の硬化性樹脂組成物の全重量を基準として、３０質量％以下が好ましい。これは、多量に混合した場合、含浸性が低下する一方、熱伝導率が高くなり、加温熱源の温風、熱水による硬化時間が長くなるためである。また、無機質骨材材料を混合した光硬化性樹脂組成物を用いた管状ライニング材では、紫外線が透過しにくくなるため特定のフィラーを少量しか混合できない。この場合、配合量は本発明の硬化性樹脂組成物の全重量を基準として、１０質量％以下が好ましい。 When using an inert fine particle and / or granular inorganic aggregate material, the amount used is the present invention in the case of a tubular lining material in which a thermosetting resin composition is impregnated into a fibrous tubular body. It is preferably 30% by mass or less based on the total weight of the curable resin composition. This is because when a large amount of the mixture is mixed, the impregnation property is lowered, the thermal conductivity is high, and the curing time by the warm air and hot water of the heating heat source is long. Further, in a tubular lining material using a photocurable resin composition mixed with an inorganic aggregate material, it is difficult for ultraviolet rays to pass through, so that only a small amount of a specific filler can be mixed. In this case, the blending amount is preferably 10% by mass or less based on the total weight of the curable resin composition of the present invention.
さらに、本発明の硬化性樹脂組成物には、鱗片状無機充填材としてガラスフレーク、マイカフレーク等を使用することができる。鱗片状無機充填材の平均粒子径は一般に１０〜４０００μｍの範囲であるが、樹脂組成物の繊維質筒状体への含浸性を維持と防食耐久性を維持するためには、平均粒子径１００〜３０００μｍ、配合量は本発明の硬化性樹脂組成物の全重量を基準として、１０質量％以下が好ましい。なお、鱗片状無機充填材としては、吸水重量安定性よりガラスフレークを用いることが好ましい。 Further, in the curable resin composition of the present invention, glass flakes, mica flakes and the like can be used as the scaly inorganic filler. The average particle size of the scaly inorganic filler is generally in the range of 10 to 4000 μm, but in order to maintain the impregnation property of the resin composition into the fibrous tubular body and the anticorrosion durability, the average particle size is 100. The compounding amount is preferably 10% by mass or less based on the total weight of the curable resin composition of the present invention. As the scaly inorganic filler, it is preferable to use glass flakes from the viewpoint of water absorption weight stability.
また、これらの熱硬化性樹脂組成物又は光硬化性樹脂組成物には、さらに顔料、酸化防止剤、流動制御剤、チキソトロピ−剤、可塑剤、収縮防止剤、消泡剤、着色剤、重合禁止剤等を必要に応じて添加することも可能である。 Further, in these thermosetting resin compositions or photocurable resin compositions, pigments, antioxidants, flow control agents, thixotropy agents, plasticizers, shrinkage inhibitors, antifoaming agents, colorants, polymerizations are further added. It is also possible to add a banning agent or the like as needed.
［ライニング材］
硬化性樹脂組成物を含むライニング材はどのような構成でもよいが、一般的には内側保護フィルム／ガラス繊維などの線維性補強材等を含む硬化性樹脂組成物／外側保護フィルムの順でこれらを積層した構成を使用することができる。ライニング材の形状は、補修対象の管路の形状に応じて、シート状や管状などに適宜成形される。繊維性補強材と硬化性樹脂組成物との重量比は４：６〜６：４の割合であることが好ましい。
[Lining material]
The lining material containing the curable resin composition may have any composition, but generally, these are in the order of the inner protective film / the curable resin composition containing the fibrous reinforcing material such as glass fiber / the outer protective film. Can be used in a laminated configuration. The shape of the lining material is appropriately formed into a sheet shape, a tubular shape, or the like according to the shape of the pipeline to be repaired. The weight ratio of the fibrous reinforcing material to the curable resin composition is preferably 4: 6 to 6: 4.
［管路補修方法］
本発明のライニング材を使用して管路を補修する方法は従来から使用されている方法で行うことができる。例えば、管路内に本発明の管状に成形したライニング材を導入した後、そのライニング材内側に空気を入れ、ライニング材の外面と管路内面を密着させた状態で、加熱または紫外線を含む光などの電磁波を照射することによりライニング材に含まれる硬化性樹脂組成物を硬化させる。その後、端部処理などの後処理を行うことで管路が補修される。補修対象の管路としては、下水道本管、取付管、マンホールなどが挙げられ、また、下水道だけでなく、老朽化したあらゆる管路に適用可能である。
[Pipeway repair method]
The method of repairing a pipeline using the lining material of the present invention can be carried out by a conventionally used method. For example, after introducing the tubular molded lining material of the present invention into a pipeline, air is introduced into the lining material, and the outer surface of the lining material and the inner surface of the pipeline are in close contact with each other, and then heated or light containing ultraviolet rays. The curable resin composition contained in the lining material is cured by irradiating with electromagnetic waves such as. After that, the pipeline is repaired by performing post-treatment such as end treatment. Examples of pipelines to be repaired include sewer mains, attachment pipes, manholes, etc., and can be applied not only to sewers but also to all aging pipelines.
本発明によれば、上述したように、架橋密度が高く、柔軟性に優れるノンスチレンのライニング剤用硬化性樹脂組成物を提供することができる。したがって、作業効率がよく、信頼性の高い管路の補修方法を提供することができる。 According to the present invention, as described above, it is possible to provide a curable resin composition for a non-styrene lining agent having a high crosslink density and excellent flexibility. Therefore, it is possible to provide a method for repairing a pipeline with good work efficiency and high reliability.
Claims (6)
（Ａ）不飽和ポリエステル樹脂またはビニルエステル樹脂、
（Ｂ）３官能以上の（メタ）アクリレートモノマー、及び
（Ｃ）重合開始剤
を含む、ライニング材用硬化性樹脂組成物。 A curable resin composition contained in a lining material for covering the inner wall surface of a pipeline.
(A) Unsaturated polyester resin or vinyl ester resin,
A curable resin composition for a lining material, which comprises (B) a trifunctional or higher functional (meth) acrylate monomer and (C) a polymerization initiator.
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| JP2024005683A JP2024036378A (en) | 2019-09-25 | 2024-01-17 | Curable resin composition for lining material, lining material, and method for repairing pipeline using the same |
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Citations (8)
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| JPH07126365A (en) * | 1993-10-29 | 1995-05-16 | Dainippon Ink & Chem Inc | Unsaturated polyester resin composition, coating material or gel coating agent, and molding material |
| JP2004156032A (en) * | 2002-10-17 | 2004-06-03 | Osaka Gas Co Ltd | Lining resin composition |
| JP2004210815A (en) * | 2002-12-26 | 2004-07-29 | Osaka Gas Co Ltd | Resin composition for lining use containing unsaturated polyester resin |
| JP2004250548A (en) * | 2003-02-19 | 2004-09-09 | Osaka Gas Co Ltd | Resin composition for lining containing unsaturated polyester resin |
| JP2007077218A (en) * | 2005-09-13 | 2007-03-29 | Yoshika Kk | Curable resin composition, lining material and tubular lining material |
| JP2012025833A (en) * | 2010-07-22 | 2012-02-09 | Daicel Corp | Fiber strengthening transparent resin composition, method of manufacturing the same, and transparent sheet |
| US20130171439A1 (en) * | 2010-09-07 | 2013-07-04 | Oded Shoseyov | Cellulose-based composite materials |
| KR20130141281A (en) * | 2012-06-15 | 2013-12-26 | 봉화토건 합자회사 | A pipe repair tube with reinforced crack- resistant property |
-
2019
- 2019-09-25 JP JP2019173809A patent/JP7429002B2/en active Active
-
2024
- 2024-01-17 JP JP2024005683A patent/JP2024036378A/en active Pending
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH07126365A (en) * | 1993-10-29 | 1995-05-16 | Dainippon Ink & Chem Inc | Unsaturated polyester resin composition, coating material or gel coating agent, and molding material |
| JP2004156032A (en) * | 2002-10-17 | 2004-06-03 | Osaka Gas Co Ltd | Lining resin composition |
| JP2004210815A (en) * | 2002-12-26 | 2004-07-29 | Osaka Gas Co Ltd | Resin composition for lining use containing unsaturated polyester resin |
| JP2004250548A (en) * | 2003-02-19 | 2004-09-09 | Osaka Gas Co Ltd | Resin composition for lining containing unsaturated polyester resin |
| JP2007077218A (en) * | 2005-09-13 | 2007-03-29 | Yoshika Kk | Curable resin composition, lining material and tubular lining material |
| JP2012025833A (en) * | 2010-07-22 | 2012-02-09 | Daicel Corp | Fiber strengthening transparent resin composition, method of manufacturing the same, and transparent sheet |
| US20130171439A1 (en) * | 2010-09-07 | 2013-07-04 | Oded Shoseyov | Cellulose-based composite materials |
| CN103370190A (en) * | 2010-09-07 | 2013-10-23 | 耶路撒冷希伯来大学伊森姆研究发展有限公司 | Cellulose-based composite materials |
| KR20130141281A (en) * | 2012-06-15 | 2013-12-26 | 봉화토건 합자회사 | A pipe repair tube with reinforced crack- resistant property |
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| JP7429002B2 (en) | 2024-02-07 |
| JP2024036378A (en) | 2024-03-15 |
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